EP0118435B1 - Verbesserte polyphenylenätherharzzusammensetzungen antistatische agenzien enthaltend - Google Patents

Verbesserte polyphenylenätherharzzusammensetzungen antistatische agenzien enthaltend Download PDF

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Publication number
EP0118435B1
EP0118435B1 EP82903010A EP82903010A EP0118435B1 EP 0118435 B1 EP0118435 B1 EP 0118435B1 EP 82903010 A EP82903010 A EP 82903010A EP 82903010 A EP82903010 A EP 82903010A EP 0118435 B1 EP0118435 B1 EP 0118435B1
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EP
European Patent Office
Prior art keywords
composition
antistatic agent
enhancer
resin
polyphenylene ether
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Expired
Application number
EP82903010A
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English (en)
French (fr)
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EP0118435A1 (de
EP0118435A4 (de
Inventor
Bruce Arthur Luxon
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General Electric Co
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General Electric Co
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/123—Polyphenylene oxides not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds
    • C08K5/19—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/02—Polyalkylene oxides

Definitions

  • polyphenylene ether resin is well known as defining a class of thermoplastic materials which possess outstanding physical properties, including hydrolytic stability, dimensional stability and excellent dielectric characteristics. Methods of preparation are known in the art and described in the patent literature, e.g., Hay, U.S. Pat. Nos. 3,306,874 and 3,306,875 and Stamatoff, U.S. Pat. Nos. 3,257,357 and 3,257,358. Other patents which show the preparation of polyphenylene ether resins include Bennett and Cooper, U.S. Pat. Nos. 3,369,656 and 3,838,102, as well as Cooper and Bennett, U.S. Pat. Nos. 3,642,699, 3,661,839 and 3,733,299.
  • thermoplastic materials having characteristic resistivities in the range of from about 10 10 to 10 12 ohms normally do not hold static charges.
  • Such static charges develop during processing and/or during normal use after molding. They are undesirable for a number of reasons: surface static charges readily attract dust and other contaminants which are unsightly and difficult to clean; often the contaminants or static charges themselves cause processing problems; the charges may accumulate to a level where an unpleasant electrical shock is imparted upon touching; in addition, a high level of static charges in a molded part covering sensitive electronic equipment may be undesirable.
  • thermoplastic resin compositions comprising a thermoplastic resin and an antistatic agent comprising a quaternary ammoniumsulfonate salt.
  • This invention involves an antistatic thermoplastic resin composition comprising a PPO resin and a minor effective amount of an antistatic agent, characterized in that it comprises:
  • the polyethylene glycol ester enhancer serves not only to improve the antistatic properties of the polyphenylene ether resin but also to reduce odor and increase impact strength. As a result, particularly desirable thermoplastic compositions are obtained.
  • any polyphenylene ether resin may be employed in the compositions of the present invention, preferred are homopolymeric or copolymeric resins having the formula: wherein the oxygen ether atom of one unit is connected to the benzene nucleus of the next adjoining unit, n represents the total number of monomer residues and is a positive integer of at least 50, e.g., from 50 to about 200 and Q, Q', Q" and Q'" are independently selected from the group consisting of hydrogen, halogen, hydrocarbon radicals, halohydrocarbon radicals having at least two carbon atoms between the halogen atoms and the phenol nucleus, hydrocarbonoxy radicals and halohydrocarbonoxy radicals having at least two carbon atoms between the halogen atom and the phenol nucleus, and Q and Q' in addition may be halogen provided that Q and Q' are preferably free of a tertiary carbon atom.
  • such resins include poly(2,6-dimethyl-1,4-phenylene)ether; poly (2,6-diethyl-1,4-phenylene)ether; poly(2-methyl-6-ethylphenylene)ether; poly(2-methyl-6-propyl-1,4-phenylene)ether; poly(2,6-dipropyl-phenylene)ether; poly(2-ethyl-6-propyl-1,4-phenylene)ether.
  • poly(2,6-dimethyl-1,4-phenylene)ether preferably having an intrinsic viscosity of from about 0.4 to 0.8, more preferably about 0.45 deciliters per gram (dl/g.) measured in solution in chloroform at 30°C.
  • compositions also desirably contain styrene resin to improve their physical properties.
  • the styrene resins preferably are those having at least 25% by weight of repeating units derived from a vinyl aromatic compound of the formula: wherein R is hydrogen, (lower)alkyl or halogen; Z is vinyl, halogen or (lower)alkyl; and p is 0 or an integer for from 1 to the number of replaceable hydrogen atoms on the benzene nucleus.
  • R is hydrogen, (lower)alkyl or halogen
  • Z vinyl, halogen or (lower)alkyl
  • p is 0 or an integer for from 1 to the number of replaceable hydrogen atoms on the benzene nucleus.
  • (lower)alkyl means alkyl of from 1 to 6 carbon atoms.
  • styrene resin as used broadly throughout this disclosure includes, by way of example, homopolymers such as polystyrene and polychlorostyrene, as well as polystyrenes which have been modified by natural or synthetic rubber, e.g., polybutadiene, polyisoprene, butyl rubber, EPDM rubber, ethylene-propylene copolymers, natural rubber, polysulfide rubbers, polyurethane rubbers and epichlorohydrin; styrene containing copolymers such as the styrene-acrylonitrile copolymers (SAN) styrene-butadiene copolymers, styrene-maleic anhydride copolymers, styrene-acrylonitrile-butadiene terpolymers (ABS), poly-a-methylstyrene, copolymers of ethylvinylbenzene and divinylbenzene; block copoly
  • the styrene resin may be present in any amount. Widely divergent proportions of from 1:99 to 99:1 by weight of polyphenylene ether resin are known. More desirably, these two resins are in a weight ratio of from about 1:5 to 5:1, most preferably about 1:1 for use in the present compositions.
  • the antistatic agent is commercially available and methods of its preparation are known. It can be prepared, for instance, by reacting approximately equimolar amounts of the corresponding tertiary amine and paratoluenemethyl sulfonate in the presence of a solvent, e.g., water, at a slightly elevated temperature, e.g., 60°-80°C, until the compound is formed.
  • a solvent e.g., water
  • the antistatic agent is present in an amount of at least 3% and preferably from 3 to 5% by weight of total thermoplastic resin. Amounts in excess of this normally do not provide any further improvements in antistatic behavior and may detract from other properties of the composition.
  • the enhancer for the antistatic agent and composition is polyethylene glycol ester.
  • the acid upon which the acid is based is relatively unimportant, the ester is most commonly of an aliphatic, preferably saturated, acid having from 2 to 5 carbons. These acids must, of course be polyfunctional; they are preferably dicarboxylic acids.
  • the enhancer desirably has a molecular weight of from about 100 to 500, with about 200 being preferred.
  • the amount of enhancer employed is not critical and may vary widely. Generally, however, a ratio of from 1:3 to 2:1, most preferably from 1:2 to 1:1 by weight of antistatic agent is present. An amount of enhancer from about 1.0 to 3% by weight of thermoplastic resin is also particularly desirable.
  • a blend premix is formed by tumbling the ingredients.
  • the blend premix is passed through an extruder at an elevated temperature, e.g., from about 300° to about 400°C., dependent on the needs of the particular composition.
  • the extrudate is cooled and chopped into pellets and the pellets are molded into any desired shape.
  • ingredients can also be included for their conventionally employed purposes. These include drip retardants, fire retardants, odor retardants, plasticizers, antioxidants, stabilizers, reinforcing agents, pigments dyes and processing aids.
  • the antistatic behaviour is measured according to the following procedure; a molded test piece is placed near finely divided cigarette ashes. The antistatic behavior is considered "good” if not even trace amounts of the cigarette ashes are attracted. The other physical properties are evaluated according to ASTM standards.
  • a resin composition is prepared by tumbling the following ingredients:
  • the resin composition is divided into six separate samples numbered 1 through 6.
  • N,N-bis-(2-hydroxyethyl)-N-octyl-N-methyl ammonium para toluene sulfonate salt antistatic agent (1) (Hexcel 106-G, produced by Hexcel Fine Chemicals) and an antistatic agent (2) comprising polyethylene glycol ester having a molecular weight of about 200 (Nocostat 2152-P manufactured by Diamond Shamrock) set forth in the Table below.
  • thermoplastic compositions of the present invention reveals a substantial improvement for the thermoplastic compositions of the present invention.
  • Example Nos. 1 and 2 some advantages for the antistatic agent (1) alone are evident. The changes in surface resistivity and antistatic behavior are clearly beneficial. In addition, some desirable increase in Izod impact strength is observable. Continuing the comparison by further reference to Example Nos. 3 and 4, it is apparent that antistatic agent (2) alone is significantly less effective. Most importantly, surface resistivity, antistatic behaviour and impact strength are not only below the respective values for the antistatic agent (1) containing composition (Example No. 2) but deteriorate further with increase in amount of antistatic agent (2) (Example Nos. 3 and 4).
  • Example Nos. 5 and 6 provided dramatic improvements in each of the foregoing properties. Moreover, in contradistinction from the above discussed trend apparent in Example Nos. 3 and 4, the addition of further agent (2) between Example Nos. 5 and 6 does not adversely affect these properties.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (8)

1. Antistatische thermoplastische Harzzusammensetzung enthaltden ein PPO-Harz und eine geringe wirksame Menge eines antistatischen Mittels, dadurch gekennzeichnet, daß sie enthält:
(a) ein Polyphenylenätherharz mit oder ohne ein Styrolharz;
(b) eine geringe, wirksame Menge eines antistatischen Mittels enthaltend eine Verbindung mit der Formel
Figure imgb0008
worin R Octyl ist und
(c) eine geringe, wirksame Menge eines Verstärkers für das antistatische Mittel (b), enthaltend ein zweites antistatisches Mittel, welches ein Polyäthylenglycolester ist.
2. Zusammensetzung nach Anspruch 1, worin der Verstärker ein durchschnittliches Molekulargewicht von 100 bis 500 aufweist.
3. Zusammensetzung nach Anspruch 2, worin der Verstärker ein Ester der aliphatischen Dicarbonsäure mit 2 bis 5 Kohlenstoffatomen ist.
4. Zusammensetzung nach Anspruch 3, worin der Verstärker und das antistatische Mittel in einem Gewichtsverhältnis von 1:3 bis 2:1 vorliegen.
5. Zusammensetzung nach Anspruch 4, worin der Verstärker in einer Menge von etwa 1,0 bis 3 Gew.-% des thermoplastischen Harzes vorliegt.
6. Zusammensetzung nach Anspruch 5, worin das antistatische Mittel in einer Menge von etwa 3 bis 5 Gew.-% des thermoplastischen Harzes vorliegt.
7. Zusammensetzung nach Anspruch 6, worin das Polyphenylätherharz die Formel
Figure imgb0009
aufweist, worin das Äthersauerstoffatom einer Einheit mit dem Benzolkern der nächsten benachbarten Einheit verbunden ist, n die Gesamtzahl der monomeren Reste bezeichnet und eine positive ganze Zahl von wenigstens 50 bezeichnet und Q, Q', Q" und Q"' unabhängig voneinander ausgewählt sind aus der Gruppe bestehend aus Wasserstoff, Halogen, Kohlenwasserstoffresten, Halogenkohlenwasserstoffresten mit wenigstens 2 Kohlenstoffatom zwischen dem Halogenatom und dem Phenylkern, Kohlenwasserstoffoxyresten und Halogenkohlenwasserstoffoxyresten mit wenigstens 2 Kohlenstoffatomen zwischen dem Halogenatom und dem Phenolkern.
8. Zusammensetzung nach Anspruch 7, worin dieselbe zusätzlich Styrolharz enthält, welches ein gummimodifiziertes hochschlagfestes Polystyrol ist.
EP82903010A 1982-09-15 1982-09-15 Verbesserte polyphenylenätherharzzusammensetzungen antistatische agenzien enthaltend Expired EP0118435B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1982/001247 WO1984001163A1 (en) 1982-09-15 1982-09-15 Improved polyphenylene ether resin compositions containing antistatic agents

Publications (3)

Publication Number Publication Date
EP0118435A1 EP0118435A1 (de) 1984-09-19
EP0118435A4 EP0118435A4 (de) 1985-02-18
EP0118435B1 true EP0118435B1 (de) 1987-12-09

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EP (1) EP0118435B1 (de)
JP (1) JPS59501509A (de)
DE (1) DE3277817D1 (de)
WO (1) WO1984001163A1 (de)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US412475A (en) * 1889-10-08 Thread-guiding device for knitting-machines
US3699066A (en) * 1971-10-08 1972-10-17 Commercial Solvents Corp Water-dispersed anionic resin compositions stabilized against agglomeration
US3933779A (en) * 1974-02-21 1976-01-20 Fine Organics Inc. Antistatic polymer blend
US4123475A (en) * 1977-12-28 1978-10-31 General Electric Company Antistatic polyphenylene ether compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Taschenbuch der Kunststoff-Additive, 1979, Carl Hanser Verlag München, Wien, P. 421, l.11, P. 424, l.16-19 *

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WO1984001163A1 (en) 1984-03-29
JPH0458503B2 (de) 1992-09-17
DE3277817D1 (en) 1988-01-21
EP0118435A1 (de) 1984-09-19
JPS59501509A (ja) 1984-08-23
EP0118435A4 (de) 1985-02-18

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